US9096725B2ActiveUtilityA1
Cross-linked polyazole, method of preparing the polyazole, electrode for fuel cell including the cross-linked polyazole, electrolyte membrane for fuel cell including the cross-linked polyazole, method of manufacturing the electrolyte membrane, and fuel cell including the cross-linked polyazole
Est. expiryApr 24, 2029(~2.8 yrs left)· nominal 20-yr term from priority
C08J 5/2256H01M 8/1081C08G 73/18H01M 8/1072C08L 65/00C08L 79/04C08G 2261/312C08G 61/12C08K 5/357C08G 2261/592C08G 2261/62H01M 8/1048C08G 2261/598C08G 2261/3241Y02E60/521H01M 8/103C08G 2261/516C08G 2261/126H01M 8/1088H01M 8/1027C08J 2379/06Y02E60/50Y02P70/50
78
PatentIndex Score
2
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References
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Claims
Abstract
A cross-linked polyazole, a method of preparing the cross-linked polyazole, an electrode and an electrolyte membrane for a fuel cell, which include the cross-linked polyazole, a method of manufacturing the electrolyte membrane, and a fuel cell including the cross-linked polyazole.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
1. A composition comprising: a polyazole including a first repeating unit comprising a repeating unit represented by one of the following formulas:
wherein Ar is selected from among the following groups:
an azole second repeating unit having at least one amino group; and a benzoxazine-based monomer, wherein, assuming that m and n represent the relative molar amount of the first repeating unit and the azole second repeating unit, respectively, in the polyazole such that m+n=1, m ranges from 0.1 to 0.9 and n ranges from 0.1 to 0.9:
and
wherein the azole second repeating unit comprises a repeating unit represented by
wherein, in Formula 2a, R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring; and
L represents a linker.
2. The composition of claim 1 , wherein the amount of the polyazole is in the range of about 40 parts to about 210 parts by weight based on 100 parts by weight of the benzoxazine-based monomer.
3. The composition of claim 1 , wherein L in Formula 2a is —CH 2 —, —C(CH 3 ) 2 —, or —C(CF 3 ) 2 —.
4. The composition of claim 1 , wherein the polyazole is a block copolymer including the first repeating unit and the second repeating unit of Formula 2a.
5. The composition of claim 1 , wherein the polyazole has a degree of polymerization of about 1 to about 900.
6. The composition of claim 1 , wherein the polyazole comprises a block copolymer represented by Formula 3 below:
wherein, in Formula 3, R 1 , R 1 ′ and R 2 are hydrogen;
Ar is selected from among the following groups:
m is a number from 0.1 to 0.9;
a is 1;
R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring;
L represents a linker;
n is a number from greater than 0 to 0.99; and
k represents a degree of polymerization of the polyazole and is a number from 10 to 300.
7. The composition of claim 1 , wherein the benzoxazine-based monomer comprises at least one compound selected from among the compounds represented by Formulae 6 through 11 below:
in Formula 6, R 1 through R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, a halogen atom, a hydroxyl group, or a cyano group; and
R 5 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbocyclic group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group,
in Formula 7, R 5 ′ is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbocyclic group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group; and
R 6 is selected from the group consisting of a substituted or unsubstituted C 1 -C 20 alkylene group, a substituted or unsubstituted C 2 -C 20 alkenylene group, a substituted or unsubstituted C 2 -C 20 alkynylene group, a substituted or unsubstituted C 6 -C 20 arylene group, a substituted or unsubstituted C 2 -C 20 heteroarylene group, —C(═O)—, and —SO 2 —,
in Formula 8, A, B, C, D and E are all carbon; or one or two of A, B, C, D and E is nitrogen and the others are carbon; and
R 1 and R 2 are linked to form a ring, wherein the ring is a C 6 -C 10 carbon ring group, a C 3 -C 10 heteroaryl group, a fused C 3 -C 10 heteroaryl group, a C 3 -C 10 heterocyclic group or a fused C 3 -C 10 heterocyclic group;
in Formula 9, A is a substituted or unsubstituted C 1 -C 20 heterocyclic group, a substituted or unsubstituted C 4 -C 20 cycloalkyl group, or a substituted C 1 -C 20 alkyl group, and wherein A includes at least one oxazine moiety; and
R 1 through R 8 are each independently a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a C 4 -C 20 cycloalkyl group, a C 1 -C 20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,
in Formula 10, R 1 and R 2 are each independently a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group or a group represented by Formula 10A below,
in Formulae 10 and 10A, R 3 is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group,
in Formula 11, at least two adjacent groups selected from among R 2 , R 3 and R 4 are linked to form a group represented by Formula 12A below, and the non-selected, remaining group is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group; and
at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked to form the group represented by Formula 12A below, and the non-selected, remaining group is a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group, and
in Formula 12A, R 1 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group; and
* denotes the sites at which the at least two adjacent groups selected from among R 2 , R 3 and R 4 of Formula 11 and the at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked, respectively.
8. A cross-linked polyazole obtained through a cross-linking reaction of the composition of claim 1 .
9. A method of preparing the cross-linked polyazole of claim 8 , the method comprising:
mixing a polyazole including a first repeating unit comprising a repeating unit represented by one of the following formulas:
wherein Ar is selected from among the following groups:
an azole second repeating unit having at least one amino group, a benzoxazine-based monomer and a phosphoric acid-based material to obtain a mixture, wherein, assuming that m and n represent the relative molar amount of the first repeating unit and the azole second repeating unit, respectively, in the polyazole such that m+n=1, m ranges from 0.1 to 0.9 and n ranges from 0.1 to 0.9; and
thermally treating the mixture,
wherein the azole second repeating unit comprises a repeating unit represented by
wherein, in Formula 2a, R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring; and
L represents a linker.
10. The method of claim 9 , wherein the thermally treating is performed at a temperature of about 60 to about 250° C.
11. The method of claim 9 , wherein the phosphoric acid-based material comprises at least one material selected from the group consisting of polyphosphoric acid, phosphonic acid (H 3 PO 3 ), ortho-phosphoric acid (H 3 PO 4 ), pyro-phosphoric acid (H 4 P 2 O 7 ), triphosphoric acid (H 5 P 3 O 10 ), meta-phosphoric acid, and a derivative thereof.
12. The method of claim 9 , wherein the polyazole including the first repeating unit and the azole second repeating unit having at least one amino group is prepared through polymerization using a material that generates phosphoric acid when hydrolyzed.
13. The method of claim 12 , wherein the material that generates phosphoric acid when hydrolyzed comprises polyphosphoric acid.
14. The method of claim 9 , wherein the polyazole including the first repeating unit and the azole second repeating unit having at least one amino group is prepared by a method comprising:
mixing biphenyl-3,3′,4,4′-tetraaminetetrahydrochloride and phosphoric acid, and thermally treating the mixture at a temperature of about 60 to about 250° C. to obtain a (2,2-(m-phenylene)-5,5-bibenzimidazole) oligomer; and
mixing the (2,2-(m-phenylene)-5,5-bibenzimidazole) oligomer with 3,4-diaminobenzoic acid and thermally treating the mixture at a temperature of about 60 to about 250° C.
15. An electrolyte membrane for a fuel cell, the electrolyte membrane comprising a composition comprising: a polyazole including a first repeating unit comprising a repeating unit represented by one of the following formulas:
wherein Ar is selected from among the following groups:
an azole second repeating unit; and a benzoxazine-based monomer, wherein, assuming that m and n represent the relative molar amount of the first repeating unit and the azole second repeating unit, respectively, in the polyazole such that m+n=1, m is a number from 0.1 to 0.9 and n is a number from 0.1 to 0.9:
and wherein the azole second repeating unit comprises a repeating unit represented by Formula 2a:
wherein, in Formula 2a, R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring; and
L represents a linker.
16. An electrolyte membrane for a fuel cell, the electrolyte membrane comprising a cross-linked polyazole obtained through a cross-linking reaction of a composition comprising: a polyazole including a first repeating unit comprising a repeating unit represented by one of the following formulae:
wherein Ar is selected from among the following groups:
an azole second repeating unit; and a benzoxazine-based monomer, wherein, assuming that m and n represent the relative molar amount of the first repeating unit and the azole second repeating unit, respectively, in the polyazole such that m+n=1, m is a number from 0.1 to 0.9 and n is a number from 0.1 to 0.9;
and
wherein the azole second repeating unit comprises a repeating unit represented by Formula 2a:
wherein, in Formula 2a, R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring; and
L represents a linker.
17. A method of manufacturing an electrolyte membrane for a fuel cell of claim 16 , the method comprising:
mixing a polyazole including a first repeating unit comprising a repeating unit represented by one of the following formulae:
wherein Ar is selected from among the following groups:
an azole second repeating unit having at least one amino group, a benzoxazine-based monomer and a phosphoric acid-based material to obtain a mixture, wherein, assuming that m and n represent the relative molar amount of the first repeating unit and the azole second repeating unit, respectively, in the polyazole such that m+n=1, m ranges from 0.1 to 0.9 and n ranges from 0.1 to 0.9;
casting the mixture on a substrate and thermally treating the cast mixture to obtain a thermally-treated product;
impregnating the thermally-treated product with the phosphoric acid-based material to obtain a resulting product; and
drying the resulting product,
wherein the azole second repeating unit comprises a repeating unit represented by Formula 2a:
wherein, in Formula 2a, R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring; and
L represents a linker.
18. The method of claim 17 , further comprising treating the thermally-treated product in a constant-temperature and constant humidity condition at a temperature of about −20 to about 30° C. and a relative humidity of about 5 to about 50%.
19. The method of claim 17 , wherein, the mixing of the polyazole including the first repeating unit and the azole second repeating unit having at least one amino group, the benzoxazine-based monomer and the phosphoric acid-based material comprises: mixing the polyazole with the phosphoric acid-based material at a temperature of about 100° C. to about 160° C. to obtain a blend, and mixing the blend with the benzoxazine-based monomer to obtain the mixture.
20. The method of claim 17 , wherein the phosphoric acid-based material comprises at least one material selected from the group consisting of polyphosphoric acid, phosphonic acid (H 3 PO 3 ), ortho-phosphoric acid (H 3 PO 4 ), pyro-phosphoric acid (H 4 P 2 O 7 ), triphosphoric acid (H 5 P 3 O 10 ), meta-phosphoric acid, and a derivative thereof.
21. The method of claim 17 , wherein the polyazole including the first repeating unit and the azole second repeating unit having at least one amino group is prepared through polymerization using a material that generates phosphoric acid when hydrolyzed.
22. The method of claim 21 , wherein the material that generates phosphoric acid when hydrolyzed comprises polyphosphoric acid.
23. The method of claim 17 , wherein the polyazole including the first repeating unit and the azole second repeating unit having at least one amino group is prepared by a method comprising:
mixing biphenyl-3,3′,4,4′-tetraaminetetrahydrochloride and polyphosphoric acid, and thermally treating the mixture at a temperature of about 60 to about 250° C. to obtain a (2,2-(m-phenylene)-5,5-bibenzimidazole) oligomer; and
mixing the (2,2-(m-phenylene)-5,5-bibenzimidazole) oligomer with 3,4-diaminobenzoic acid and thermally treating the mixture at a temperature of about 60 to about 250° C.
24. An electrode for a fuel cell, the electrode comprising the composition of claim 1 .
25. An electrolyte for a fuel cell, the electrolyte comprising the cross-linked polyazole of claim 8 .
26. A fuel cell comprising:
a cathode;
an anode; and
an electrolyte membrane according to claim 15 disposed between the cathode and the anode.
27. A fuel cell comprising:
a cathode;
an anode; and
an electrolyte membrane according to claim 16 disposed between the cathode and the anode.
28. The electrolyte membrane of claim 15 , wherein the amount of the polyazole is in the range of about 40 parts to about 210 parts by weight based on 100 parts by weight of the benzoxazine-based monomer.
29. The electrolyte membrane of claim 15 , wherein L in Formula 2a is —CH 2 —, —C(CH 3 ) 2 —, or —C(CF 3 ) 2 —.
30. The electrolyte membrane of claim 15 , wherein the polyazole is a block copolymer including the first repeating unit and the second repeating unit of Formula 2a.
31. The electrolyte membrane of claim 15 , wherein the polyazole has a degree of polymerization of about 1 to about 900.
32. The electrolyte membrane of claim 15 , wherein the polyazole comprises a block copolymer represented by Formula 3 below:
wherein, in Formula 3, R 1 , R 1 ′ and R 2 are hydrogen;
Ar is selected from among the following groups:
m is a number from 0.1 to 0.9;
a is 1;
R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring;
L represents a linker;
n is a number from 0.1 to 0.9; and
k represents a degree of polymerization of the polyazole and is a number from 10 to 300.
33. The electrolyte membrane of claim 15 , wherein the benzoxazine-based monomer comprises at least one compound selected from among the compounds represented by Formulae 6 through 11 below:
in Formula 6, R 1 through R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, a halogen atom, a hydroxyl group, or a cyano group; and
R 5 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbocyclic group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group,
in Formula 7, R 5 ′ is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbocyclic group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group; and
R 6 is selected from the group consisting of a substituted or unsubstituted C 1 -C 20 alkylene group, a substituted or unsubstituted C 2 -C 20 alkenylene group, a substituted or unsubstituted C 2 -C 20 alkynylene group, a substituted or unsubstituted C 6 -C 20 arylene group, a substituted or unsubstituted C 2 -C 20 heteroarylene group, —C(═O)—, and —SO 2 —,
in Formula 8, A, B, C, D and E are all carbon; or one or two of A, B, C, D and E is nitrogen and the others are carbon; and
R 1 and R 2 are linked to form a ring, wherein the ring is a C 6 -C 10 carbon ring group, a C 3 -C 10 heteroaryl group, a fused C 3 -C 10 heteroaryl group, a C 3 -C 10 heterocyclic group or a fused C 3 -C 10 heterocyclic group;
in Formula 9, A is a substituted or unsubstituted C 1 -C 20 heterocyclic group, a substituted or unsubstituted C 4 -C 20 cycloalkyl group, or a substituted C 1 -C 20 alkyl group, and wherein A includes at least one oxazine moiety; and
R 1 through R 8 are each independently a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a C 4 -C 20 cycloalkyl group, a C 1 -C 20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,
in Formula 10, R 1 and R 2 are each independently a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group or a group represented by Formula 10A below,
in Formulae 10 and 10A, R 3 is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group,
in Formula 11, at least two adjacent groups selected from among R 2 , R 3 and R 4 are linked to form a group represented by Formula 12A below, and the non-selected, remaining group is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group; and
at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked to form the group represented by Formula 12A below, and the non-selected, remaining group is a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group, and
in Formula 12A, R 1 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group; and
* denotes the sites at which the at least two adjacent groups selected from among R 2 , R 3 and R 4 of Formula 11 and the at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked, respectively.
34. The electrolyte membrane of claim 16 , wherein the amount of the polyazole is in the range of about 40 parts to about 210 parts by weight based on 100 parts by weight of the benzoxazine-based monomer.
35. The electrolyte membrane of claim 16 , wherein L in Formula 2a is —CH 2 —, —C(CH 3 ) 2 —, or —C(CF 3 ) 2 —.
36. The electrolyte membrane of claim 16 , wherein the polyazole is a block copolymer including the first repeating unit and the second repeating unit of Formula 2a.
37. The electrolyte membrane of claim 16 , wherein the polyazole has a degree of polymerization of about 1 to about 900.
38. The electrolyte membrane of claim 16 , wherein the polyazole comprises a block copolymer represented by Formula 3 below:
wherein, in Formula 3, R 1 , R 1 ′ and R 2 are hydrogen; Ar is selected from among the following groups:
m is a number from 0.1 to 0.9;
a is 1;
R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring;
L represents a linker;
n is a number from 0.1 to 0.9; and
k represents a degree of polymerization of the polyazole and is a number from 10 to 300.
39. The electrolyte membrane of claim 16 , wherein the benzoxazine-based monomer comprises at least one compound selected from among the compounds represented by Formulae 6 through 11 below:
in Formula 6, R 1 through R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, a halogen atom, a hydroxyl group, or a cyano group; and
R 5 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbocyclic group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group,
in Formula 7, R 5 ′ is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbocyclic group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group; and
R 6 is selected from the group consisting of a substituted or unsubstituted C 1 -C 20 alkylene group, a substituted or unsubstituted C 2 -C 20 alkenylene group, a substituted or unsubstituted C 2 ′ C 20 alkynylene group, a substituted or unsubstituted C 6 -C 20 arylene group, a substituted or unsubstituted C 2 -C 20 heteroarylene group, —C(═O)—, and —SO 2 —,
in Formula 8, A, B, C, D and E are all carbon; or one or two of A, B, C, D and E is nitrogen and the others are carbon; and
R 1 and R 2 are linked to form a ring, wherein the ring is a C 6 -C 10 carbon ring group, a C 3 -C 10 heteroaryl group, a fused C 3 -C 10 heteroaryl group, a C 3 -C 10 heterocyclic group or a fused C 3 -C 10 heterocyclic group;
in Formula 9, A is a substituted or unsubstituted C 1 -C 20 heterocyclic group, a substituted or unsubstituted C 4 -C 20 cycloalkyl group, or a substituted C 1 -C 20 alkyl group, and wherein A includes at least one oxazine moiety; and
R 1 through R 8 are each independently a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a C 4 -C 20 cycloalkyl group, a C 1 -C 20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,
in Formula 10, R 1 and R 2 are each independently a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group or a group represented by Formula 10A below,
in Formulae 10 and 10A, R 3 is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group,
in Formula 11, at least two adjacent groups selected from among R 2 , R 3 and R 4 are linked to form a group represented by Formula 12A below, and the non-selected, remaining group is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group; and
at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked to form the group represented by Formula 12A below, and the non-selected, remaining group is a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group, and
in Formula 12A, R 1 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group; and
* denotes the sites at which the at least two adjacent groups selected from among R 2 , R 3 and R 4 of Formula 11 and the at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked, respectively.
40. The membrane of claim 15 , wherein the molar ratio of the first repeating unit to the second repeating unit is about 8:2, about 5:5, or about 2:8.
41. The membrane of claim 16 , wherein the molar ratio of the first repeating unit to the second repeating unit is about 8:2, about 5:5, or about 2:8.
42. The membrane of claim 16 , wherein the benzoxazine-based monomer comprises at least one compound selected from among the compounds represented by Formulae 6 through 11:
in Formula 6, R 1 , R 2 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, a halogen atom, a hydroxyl group, or a cyano group;
R 3 is independently a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a halogen atom, a hydroxyl group, or a cyano group; and
R 5 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbocyclic group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group,
in Formula 7, R 5 ′ is a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 6 -C 20 aryloxy group, or a substituted or unsubstituted C 2 -C 20 heteroaryloxy group; and
R 6 is selected from the group consisting of a substituted or unsubstituted C 1 -C 20 alkylene group, a substituted or unsubstituted C 2 -C 20 alkenylene group, a substituted or unsubstituted C 2 -C 20 alkynylene group, a substituted or unsubstituted C 6 -C 20 arylene group, a substituted or unsubstituted C 2 -C 20 heteroarylene group, —C(═O)—, and —SO 2 —,
in Formula 8, A, B, C, D and E are all carbon; or one or two of A, B, C, D and E is nitrogen and the others are carbon; and
R 1 and R 2 are linked to form a ring, wherein the ring is a C 6 -C 10 carbon ring group, a C 3 -C 10 heteroaryl group, a fused C 3 -C 10 heteroaryl group, a C 3 -C 10 heterocyclic group or a fused C 3 -C 10 heterocyclic group;
in Formula 9, A is a substituted or unsubstituted C 1 -C 20 heterocyclic group, a substituted or unsubstituted C 4 -C 20 cycloalkyl group, or a substituted C 1 -C 20 alkyl group, and wherein A includes at least one oxazine moiety; and
R 1 through R 8 are each independently a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a C 4 -C 20 cycloalkyl group, a C 1 -C 20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,
in Formula 10, R 1 and R 2 are each independently a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group or a group represented by Formula 10A below,
in Formulae 10 and 10A, R 3 is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group,
in Formula 11, at least two adjacent groups selected from among R 2 , R 3 and R 4 are linked to form a group represented by Formula 12A below, and the non-selected, remaining group is a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group; and
at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked to form the group represented by Formula 12A below, and the non-selected, remaining group is a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 6 -C 20 aryloxy group, a halogenated C 6 -C 20 aryl group, a halogenated C 6 -C 20 aryloxy group, a C 1 -C 20 heteroaryl group, a C 1 -C 20 heteroaryloxy group, a halogenated C 1 -C 20 heteroaryl group, a halogenated C 1 -C 20 heteroaryloxy group, a C 4 -C 20 carbon ring group, a halogenated C 4 -C 20 carbon ring group, a C 1 -C 20 heterocyclic group or a halogenated C 1 -C 20 heterocyclic group, and
in Formula 12A, R 1 is a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 2 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 4 -C 20 carbon ring group, a substituted or unsubstituted C 4 -C 20 carbocyclic alkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a substituted or unsubstituted C 2 -C 20 heterocyclic alkyl group; and
* denotes the sites at which the at least two adjacent groups selected from among R 2 , R 3 and R 4 of Formula 11 and the at least two adjacent groups selected from among R 5 , R 6 and R 7 are linked, respectively.
43. An electrolyte membrane for a fuel cell, the electrolyte membrane comprising a cross-linked polyazole obtained through a cross-linking reaction of a composition comprising: a polyazole including a first repeating unit comprising a repeating unit represented by one of the following formulae:
wherein Ar is selected from among the following groups:
an azole second repeating unit; and a benzoxazine-based monomer, wherein, assuming that m and n represent the relative molar amount of the first repeating unit and the azole second repeating unit, respectively, in the polyazole such that m+n=1, m is a number from 0.1 to 0.9 and n is a number from 0.1 to 0.9:
wherein the azole second repeating unit comprises a repeating unit represented by Formula 2a:
wherein, in Formula 2a, R 3 , R 3 ′, R 3 ″, R 3 ′″, R 4 , R 4 ′, R 4 ″, R 5 , R 5 ′, and R 5 ″ are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, wherein R 1 and R 2 may be linked to form a C4-C20 carbon ring or a C3-C20 hetero ring; and
L represents a linker, and
wherein the benzoxazine-based monomer comprises at least one compound selected from:Cited by (0)
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